ANALYTICAL CHEMISTRY Based on the German text or F. P. TREADWELL, Pu.D., Professor of Analytical Chemistry at the Polytechnic Institute of Zarich TRANSLATED AND REVISED BY WILLIAM T. HALL, 8.B., Assistant Professor of Analytical Chemistry, Massachusetts Institute of Technology Votume I QUALITATIVE ANALYSIS FOURTH ENGLISH AFTER THE EIGHTH GERMAN EDITION TOTAL ISSUE, TWENTY-ONE THOUSAND NEW YORK JOHN WILEY & SONS, Ino. Lonvon: CHAPMAN & HALL, LiwrrepCopyright, 1903, 1906, 1913, 1916 ay WILLIAM T. HALL First and Second Editions Entered at Stationers’ Hall 3/20 soon wanurserurensPREFACE TO THE FOURTH ENGLISH EDITION Tue German text upon which this book is based was written by an American who has taught for many years at Zurich. The first English edition appeared as an authorized translation by one who had been teaching analytical chemistry for only three years at that time. Tt was translated largely as a result of a chance remark of his assist- ant, R. W. Balcom, who deplored the fact that the students could not read German readily enough to make use of the German text as a reference book. At that time, the translator was using, as he has always used, the excellent book of A. A. Noyes as a laboratory manual in Qualitative Analysis and the extremely useful text of H. P. Talbot for the preliminary work in Quantitative Analysis. The results obtained by asking the students to purchase both volumes of this book in addition have been exceedingly gratifying. Better examination papers have resulted and there have been fewer unneces- sary questions asked in the laboratory. Recently Professor Noyes has greatly changed his text on Quali- tative Analysis and this has unquestionably had considerable influence upon the preparation of the fourth English edition of this book. It has been so thoroughly revised and so largely rewritten that it is no longer fair to Professor Treadwell to publish the book as a literal translation, although the writer remains in thorough sympathy with Professor Treadwell’s views and does not wish, in any way, to dis- claim the great benefit and inspiration he has derived from close study of the original text. He must, however, express his obligation to other texts, particularly to those of Noyes, Stieglitz, Béttger, and Ostwald, from which many of the ideas introduced into this text have been copied. The general plan of the book has been kept the same, but greater stress has been laid upon the theoretical side of the subject, particularly with regard to the applications of the mass action prin- ciple, the ionization theory, and the theory of oxidation and reduction. * The translator wishes to acknowledge his indebtedness to Mr. Donald Belcher, who has read all the proofs of this edition and offered many valuable suggestions. Wiuram T. Haw. Massacnuserts Instrrure or TEcaNowocy, February, 1916. iiiPREFACE TO THE FIRST EDITION Havina been repeatedly requested by former pupils to publish the lectures on Analytical Chemistry given by me at this Institute since 1882, and not having time then to do it myself, I permitted the “ Verein der Polytechniker ” in 1885 to print in manuscript form the notes of one of my students. This output met with such a friendly reception that in 1888 a second edition became necessary. Subsequently I decided to revise the material thoroughly and publish it in book form; this text-book of Analytical Chemistry represents, therefore, a somewhat amplified repetition of my lectures. The book is intended not only for laboratory use, but also for self-study. With each element the mineralogical occurrence, erys- talline form, and isomorphous rélations are briefly mentioned. Then, after explaining the reactions, the methods of separation are given in the form of tables; because, contrary to the views of many, I have in this way obtained the best results in teaching. These tables are summarized charts by which the student can quickly find his bearings. Much weight is placed upon the determination of the sensitive- ness of the single reactions, as explained on page 75, because the beginner becomes in this way at once familiar with the solubility of the most important salts, and also with simple stoichiometrical calculations. ‘The approximate solubility of potassium chloroplatin- ate, for example, is found from the following determination of the sen- sitiveness of the reaction by which it is formed: If 100 ce. of the solution contain 0.156 gm. potassium, one finds that the formation of the chloroplatinate, at ordinary temperatures, only takes place on addition of a little alcohol; but on increasing slightly the amount of potassium in the solution, it takes place imme- diately. We can, therefore, assume that the solution, which con- vvi PREFACE TO THE FIRST EDITION tains 0.156 gm. of potassium per 100 cc. water, is saturated with chloro- platinate; hence the amount of the latter may be calculated: .156 : 23 .156 + 2; z=0.97. Thé result shows that 100 cc. of water, at ordinary temperatures, dissolve 0.97 gm. of KePtCls, while accurate determinations at 20° C. have given the value 1.12, The difference, about 12 per cent, is explained by the facts that we did not work at exactly 20° C., nor with absolutely pure water; the solution also contains an excess of chloroplatinic acid, whereby the solubility of the potassium chloro- platinate is diminished; evidently the values obtained in this way permit a very good comparison of the solubilities of the different salts. From the sensitiveness of the reaction between a potassium salt and tartaric acid, the solubility of the potassium acid tartrate may be found to be 0.38; so that the solubility of the potassium chloroplatinate is to that of the potassium acid tartrate as 0.97 : 0.38; the potassium tartrate is about three times as insoluble as the chloro- platinate, ete. The size of the book does not permit going into the microchemi- cal detection of the different elements. We have, however, in the excellent work of H. Behrens, “ Anleitung zur mikrochemischen Analyse,” a reference book of the highest rank. In publishing this, the first volume of the work, I beg of my col- leagues and fellow chemists to kindly inform me of any errors or omissions. F, P. TREADWELL. Zuruce, April 29, 1899,a Intexnationat Atomic WeiauTs, 1916 Atomic | Symbol | Atomic Symbol | Atom Al a Mo 96.0 Sb 120.2 Nd 144.3 A 39.88 Ne 20.2 As 74.96 Ni 58.68 Ba 137.37 N 14.01 Bi 208.0 Os 190.9 B 11.0 ° 16.00 Br 79.92 Pa 106.7 Ca 112.40 P 31.04 Cs 182.81 |} Platinum Pt 195.2 Ca 40.07 || Potassium. K 39.10 Cc Pr 140.9 Ce Ra 226.0 cl Rh 102.9 Cr Rb 85.45 Co Ru | 101.7 Cb Sa, 150.4 Cu Be 44.1 Dy Se 79.2 Er Si 28.3 Eu Ag 107.88 F Na 23.00 Ga Strontium, Sr 87.63 Ga 69.9 Sulfur. 8 32.06 Ge 72.5 Tantalum... Ta 181.5 Gl 9.1 |) Tellurium. Te 127.5 Au 197.2 || Terbium. To | 159.2 He 4.00 || Thallium ‘Tl 204.0 H 1.008 |] Thorium. Th =| 232.4 In 114.8 || Thulium. Tm | 168.5 I 126.92 Sn 18.7 Ir 193.1 Ti 48.1 Fe 55.84 Ww 184.0 Kr 82.92 ay 238.2 La 139.0 |] Vanadium . v 51.0 Pb 207.20. |] Xenon. Xe | 130.2 Li 6.94 || Ytterbium. . Lu 175.0 (Neoytterbium) Bas) 173.5 Mg 24.32 |] Yttrium, Yt 88.7 Mn 54.93 |] Zine. Zn 65.37 Hg | 200.6 |) Zirconium... Dr 90.6 1 Also called Beryllium, Be.TABLE OF CONTENTS PART I GENERAL PRINCIPLES PAGE Spectroscopic Chart. Frontispiece International Atomic Weights, 1916. . 7 Qualitative and Quantitative Analysis 1 Reactions in the Wet Way 1 Theory of Electrolytic Dissociation. 4 Tonization of Common Electrolytes... 10 Nomenclature of the Ions. 10 Equilibrium between a Solid and a Liquid. u Chemical Equilibrium and the Mass Action La 13 Equilibrium between a Solid and Two Liquids... .. Ww Influence of Changes in Concentration upon Ionization. 18 Solubility Product. 9 Complex Ions... 2 Reactions of the Ions. 26 Oxidation and Reduction. . 27 Electromotive Series and Oxidation Potentials 37 ‘The Effect of a Common Ion. 45 Hydrolysis. 48 Amphoterie Blectrolytes 52 Detection of Acids and Bases. ‘Theory of Indicator 54 Evaporation of Acids... 56 Filtration and Washing Precipitates, 58 Colloidal Solutions. 58 Reactions in the Dry Way. 61 Division of the Metals into Groups. 70 Concentrations of Reagents. Dan Determination of Sensitiveness of Reactions... . | io PART II REACTIONS OF THE METALS (CATIONS) Group V (AtKALIES) Potassium. 78 Sodium, 82 Ammonium 87 Magnesium 93 Separation of the Metals of Group V. 96